Catalytic hydroamination of alkynes and norbornene with neutral and cationic tantalum imido complexes

Organic Letters

Volumn 6, Issue 15, 2004, Pages 2519-2522

  Anderson, Laura L ^a   Arnold, John ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE; HISTAMINE; NORBORNENE DERIVATIVE; TANTALUM;

AMINATION; ARTICLE; ARYLATION; CATALYSIS; CHEMICAL REACTION; STOICHIOMETRY; SYNTHESIS;

ALKYNES; AMINATION; CATALYSIS; INDICATORS AND REAGENTS; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE; NORBORNANES; ORGANOMETALLIC COMPOUNDS; TANTALUM;

EID: 4043055327     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0492851     Document Type: Article

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39. The cause of higher activity in the in situ generated complex is presently unknown; unfortunately, neither the cationic complex nor any subsequent intermediates can be observed using NMR spectroscopy due to constraints of instantaneous reactivity and insolubility, respectively.
40. This compound has already been shown to catalyze the hydroamination of 1-hexyne. See ref 8.
41. 1H NMR but decomposes before the reaction goes to completion. Low yields of product caused by oligomerization of phenylacetylene have also been observed by Odom and co-workers (see ref 5a). Low yields and Markovnikov selectivity were also observed by Vendier and co-workers (see ref 8).
42. Preliminary results indicate that the catalyst decomposes to a tantalum imido cluster within 24 h.
43. Compound 1b showed no reactivity when treated with a mixture of norbornene and aniline.
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45. Preliminary GC-MS results indicate that electron-withdrawing substituents on aniline favor formation of 10 while electron-donating substituents favor formation of 11.
46. 2 confirmed the assignment of the protons in question.